O-quinolyl-(8)-n-methyl carbamic acid esters



United States Patent 3,362,960 O-QUINOLYL-(Q-N-METHYL CARBAMIC ACIDESTERS Ernst Hodel, Basel, Switzerland, assignor to Geigy 'ChemicalCorporation, Greenburgh, N.Y., a corporation of Delaware No Drawing.Continuation of application Ser. No. 457,808, May 21, 1965. Thisapplication Apr. 24, 1967, Ser. No. 633,304 Claims priority, applicationSwitzerland, June 4, 1964, 7,290/ 64 9 Claims. (Cl. 260-287) This is acontinuation of copending application Ser. No. 457,808, filed May 21,1965, now abandoned.

The present invention concerns new heterocyclic carbamic acid esters andthe salts thereof, particularly quinolyl-(8)-carbamic acid esters,processes for the production thereof as well as fungicidal agents whichcontain these new compounds and/or their salts as active ingredients,also processes for combatting phytopathogenic fungi using the newcompounds and/ or the salts thereof as active ingredients or usingagents which contain them as active ingredients, as well as processesfor the production of such fungicidal agents.

It has been found that, due to their excellent fungicidal activity,heterocyclic carbamic acid esters of the formula wherein R and X eachrepresent hydrogen or a lower aliphatic hydrocarbon radical,

Y represents a monovalent substituent as defined below,

and

each of Q and Z represents hydrogen, an optionally substituted aliphaticradical as defined below, or halogen,

and are suitable for the combatting of fungi, in particular for thecombatting of photopathogenic fungi.

In contrast thereto, known quinonyl N-methyl carbamic acid esterpossesses no practically useful fungicidal activity.

Lower used herein in connection with an aliphatic radical means thatsuch radical has from 1 to 4 carbon atoms, unless expressly statedotherwise.

The new heterocyclic carbamic acid esters of Formula I are producedaccording to the invention by reacting a compound of the formula whereinR, Q, X, Y and Z have the meaning given above, with an N-methyl carbamicacid halide, particularly with N-methyl carbamic acid chloride.

The reaction is optionally performed in the presence of a solvent whichis inert to the reaction partners such as an aromatic hydrocarbon, e.g.benzene, toluene, xylene, an aliphatic or aromatic chlorinatedhydrocarbon, as ester, ketone or amide and it is performedadvantageously in the presence of a proton acceptor such as an organicbase, e.g. a tertiary amine such as pyridine or trialkylamine, aninorganic base, e.g. an alkyli or alkaline earth metal hydroxide. Thereaction temperatures range from 10l00 C. Instead of the preferredN-methyl carbamic acid chloride, also N-rnethyl carbamic acid bromidecan be reacted with the starting materials of Formula II.

The new carbamic acid esters of Formula I are also obtained by amodified process by reacting the starting materials of Formula II withmethyl isocyanate instead of with an N-methyl carbamic acid halide.

Another variation of the invention consists in the use of a mixture ofmethyl isocyanate and N-methyl carbamic acid chloride instead of methylisocyanate in the process described immediately above.

The new heterocyclic carbamic acid esters of Formula I can also beobtained by reacting a compound of Formula II with phosgene andmethylamine, or by treating these starting materials with chloroforrnicacid ethyl ester and then reacting the product obtained withmethylarnine. The reactions described in all these modifications of theprocess are also performed advantageously in the presence of solventswhich are inert to the reaction components and a proton acceptor.Aromatic hydrocarbons such as benzene, toluene, xylene, etc. and alsochlorinated hydrocarbons such as chloroform, chlorobenzene, also amidessuch as dimethyl formamide, or ketones can be used as solvents. Suitableproton acceptors are the inorganic bases such as the hydroxides ofalkali and alkaline earth metals and organic nitrogen bases, e.g.tertiary amines such as triethylamine and pyridine.

If desired, the carbamic acid esters of Formula I produced by theprocess and variations thereof described above, can be converted intotheir salts, especially their non-phytotoxic salts, by reaction withorganic or inorganic acids, e.g. with hydrochloric acid, sulfuric acid,nitric acid, acetic acid, propionic acid, benzoic acid, phthalic acid,oxalic acid, succinic acid or citric acid.

Starting compounds of Formula II are known or can be readily produced inan analogous manner as the known compounds, by known methods.

The new carbamic acid esters of Formula I are stable in Water anddissolve well in the usual organic solvents.

By lower aliphatic hydrocarbon radicals symbolized by R and X in FormulaI are meant alkyl and alkenyl radicals having 1 to 6 carbon atoms,preferably those having 1-4 carbon atoms such as the methyl and ethylradical, the propyl and butyl radicals, the allyl and methally radical,the butenyl radicals. As optionally substituted aliphaticradicals-symbolized by Q or Zare meant the alkyl and alkenyl radicalslisted for R and X which can be substituted by one or more halogen atomssuch as fluorine, chlorine or bromine, by the hydroxyl or amino group,the phenyl, a halogenophenyl or nitrophenyl radicaL Examples ofmonovalent substituents, symbolized by Y in Formula I, are: hydrogen,alkyl and alkenyl radicals having 1-5 carbon atoms; aryl radicals, e.g.the phenyl, nitrophenyl and halogenophenyl radicals; aralkyl radicalssuch as the benzyl radical; alkoxy, alkylthio, alkenyloxy andalkenylthio radicals the hydrocarbon moiety of which contains 1 tocarbon atoms; aliphatic and aromatic acyl radicals, namely alkanoyl ofmaximally 18 carbon atoms, such as the acetyl, propionyl, butyryl,valeryl, lauroyl, stearoyl radical, etc., as well as the benzoyl andphenacyl radicals and derivatives thereof substituted by halogen, thenitro, alkyl or alkoxy groups; halogen atoms such as fluorine, chlorine,bromine, iodine; halogenoalkyl radicals such as the trifiuoromethylradical; the amino group; an alkylamino, dialkylamino or acylarninogroup; the cyano or thiocyano group, the nitro group, the sulfinyl,sulfonyl, or sulfamyl radical and also an alkylsulfonamido radical.

The aliphatic hydrocarbon radicals represented 'by R and X can beidentical or ditferent.

The new active ingredients of Formula I have excellent activity againstnumerous phytopathogenic fungi and are used in the form of fungicidesfor the protection of plants and parts thereof by which is meantblossom, seeds, fruit, roots, stalks and foliage. Because of theirproperties, the new active substances are both protective fungicides andalso systemic fungicides. Plants treated with the active substancesaccording to the invention are given an additional and more long lastingprotection from attack by fungi. For the treatment and protection ofseeds, the compounds of Formula I-made up into so-called seeddressingshave good activity particularly in the case of attack by Tilletia tritici and Fusarium culmorum.

There is no inhibition of germination of the seeds treated. The newcarbamic acid esters have no phytotoxic effects on plants in the normalconcentrations for application, which vary between 0.01 and 2%(calculated on the active substance). In addition to the excellentfungicidal activity, the compounds of Formula I also have fungistaticproperties so that they can be used for the combatting of fungi onmaterials of all types either alone or combined with other substancessuitable for the protection of material. In addition, the new carbamicacid esters can be used for combatting certain pests as has been shown,for instance, in tests on ixodes (Rhipocephalus bursa and Boophilusmicroplus).

Particularly satisfactory fungicidal action is shown by the compoundsfalling under Formula I in which R represents hydrogen or methyl,

X represents hydrogen or lower alkyl,

Y represents hydrogen, lower alkyl, lower alkoxy, alkanoyl of from 2 to12 carbon atoms, benzoyl, chlorobenzoyl, 'bromobenzoyl, chlorine,bromine, flourine, iodine, nitro, thiocyano, cyano or amino,

Z represents hydrogen, chlorine, bromine, fluorine, io-

dine, lower alkyl, alkenyl of from 3 to 4 carbon atoms, benzyl,chlorobenzyl orbromobenzyl, and

Q represents hydrogen, chlorine or bromine.

The following non-limitative examples serve to illustrate the invention.Where not otherwise stated, parts and percentages are given therein asby weight and the temperatures are in degrees Centigrade.

Example 1 31.8 parts of 2-methyl-S-hydroxyquinoline are dissolved in 150parts by volume of dimethyl form-amide and 40 parts of pyridine(anhydrous). A solution of 40 parts of N-methyl carbamic acid chloridein 60 parts of dimethyl formamide are added dropwise at a temperature ofl5 while cooling well, the addition being made within minutes. Thereaction mixture is then stirred for 6 hours at room temperature. Thetemperature is then raised to 50-55 and the mixture is stirred for 15hours at this temperature. To determine whether the reaction has beencompleted, a sample is taken from the reaction mixture, diluted withethanol and a few drops of very dilute aqueous solution of ferricchloride are added. If the reaction is complete, the colour should onlybe a pale green. The reaction mixture is cooled and poured into icewater while stirring. A precipitate is formed which is filtered undersuction and washed with ice water. The crude product is dried in vacuoat room temperature. After recrystallisation from benzene, the O-[2i-tmethyl-quinolyl-(S)]-N-methyl carbamic acid ester obtained melts at136-138" (with decomposition). The yield is 56% of the theoretical.

Example 2 191 parts of 2-methyl-8-hydroxyquinoline are dissolved in 800parts by volume of dimethyl formamide and 300 parts of anhydroustriethylamine. A solution of 190 parts of methyl carbamic acid chlorideand 50 parts of methyl isocyanate in 200 parts of dimethyl formamide isadded dropwise to this solution within 30 minutes. The mixture is thenstirred for 2 hours at room temperature. The completion of the reactionis determined with iron-III chloride as described in Example 1. Thereaction mixture is then slowly poured into ice water while stirringwell. The precipitate formed is filtered off under suction and washedwith ice water. Recrystallised from benzene, the O-[Z-methylquinolyl-(S) J-N-rnethyl carbamic acid ester so obtained melts at136138 (with decomposition). The yield is 62% of the theoretical.

Example3 parts of N-methyl carbamic acid chloride dissolved in 100 partsby volume of dimethyl formamide, are added dropwise within about half anhour to a suspension of 151.5 parts of 5,7-dibromo-8-hydroxyquinoline in500 parts by volume of dimethyl formamide and 100 parts of anhydrouspyridine, the addition being made while stirring at 10-15". The mixtureis stirred for 6 hours at room temperature and then for another 15 hoursat 4050, whereupon a brown liquid is obtained. The end of the reactionis determined as described in Example 1 with a solution of ferricchloride. The clear reaction mixture, after cooling, is poured in 6000parts of water while stirring. After 3 hours, the reaction product whichprecipitates is filtered off under suction, washed with water, quicklydried in vacuo over a drying agent and recrystallised from abs. benzene.The O-[5,7-dibrornoquinolyl- (8)]-N-methyl carbamic acid ester isobtained in the form of colourless needles which melt at 202203. Theyield is 82.2% of the theoretical.

Example 4 21.5 parts of 5-n-butyryl-8-hydroxyquinoline are dissolved in100 parts by volume of dimethyl formamide. After adding 20 parts ofanhydrous pyridine, 20 parts of methyl carbamic acid chloride dissolvedin 50 parts by volume of dimethyl formamide are added dropwise within 10minutes at 10-15 while stirring. The mixture is stirred for 24 hours atroom temperature and the end of the reaction is determined as describedin Example 1. The brown reaction liquid is poured into 1500 parts of icewater and stirred for 2 hours in order to decompose the excess methylcarbamic acid chloride. The solid reaction product which precipitates isfiltered off under suction, washed with water and dried. Afterrecrystallisation from benzene/petroleum ether, the0[5-n-butyryl-quinolyl- (8)]-N-methyl carbamic acid ester obtained meltsat -107". The yield is 62.5% of the theoretical.

The compounds given in the following table are also obtained by themethods described in the above examples on 115121; the corresponding8-hydroxyqumol1ne derivatives:

Ex. Compound M.P., Yield, No. 0. Percent 5O[5-methyl-quino1yl-(8)l-N-Inethyl 148-149 66. 6

carbamic acid ester.

6- O-[2,fi-dimethyl-quinolyl-(8)1-N-methyl 146-147 52. 1

carbamic acid ester.

7 O-[5-ethyl-quinolyl-(8)]-N-methyl car- 123-126 86. 9

bamic acid ester.

8. O-[3-methyl-quh1olyl-(8)]-N-Inethy1 car- 143-144 55.

barnic acid ester.

9- O-[3-ethyl-quinolyl-(8)1-N-methyl car- 125-127 43. 4

bamic acid ester.

10. O-[2-1nethyl-5-ethyl-quinolyl-(S)]-N- 139-141 53. 2

methyl carbamic acid ester.

11 O-[-acetyl-quinolyl-(8)]-N-methyl car- 119-121 43. 0

bamic acid ester.

12- O-[5-isovaleryl-quinolyl-(8)]-N-methyl 104-105 59. 4

carbamic acid ester.

13 O-[5-benzoyl-quinolyl-(8)]-N-methyl car- 128-129 60. 7

barnic acid ester.

14- O-[5-(2-chloroh enzoyl)-quinolyl-(8)]- 113-115 48. 9

N-methyl carbamic acid ester.

15 l O-[5-(4-chlorobcnzoyl)-quinolyl-(8)]-N- 216-217 44. 6

methyl carbamic acid ester.

16. O-[5-(2-bromobenzoyl) -quinolyl-(8)]-N- 116-118 31. 6

methyl-carbamic acid ester.

17 O-[5-(4-bromobenzoyl)-quinolyl-(8)]-N- 213-215 47. 2

methylcarbamic acid ester.

18- O-[5-(2 ,4-dicl1lorobenzoyl)-quinolyl-(8)]- 1 125 42. 5

N-methyl carbamic acid ester.

19- O-[2-methyl-5-acetyl-quinolyl-(8)]-N- 129-131 50. 3

methyl carbamic acid ester.

20 O-[2-methyl-5 isovaleryl-quinolyl-(8)} 108-109 36. 6

N-methyl carbamic acid ester.

21 O-[Z-methyl-fi-lauroyl-quinolyl-(8)]-N- 87-90 36. 1

methyl carbarnic acid ester.

22- O-[2-methyl-5-benzoyl-quinolyl-(8)]-N- 152-154 33. 4

methyl carbamic acid ester.

23- O-[2-methyl-5-(4-chlorobenzoyl) -quino- 134-135 23. 3

lyl-(8)]N-methyl carbamic acid ester.

24. O-[5-chloroquinolyl-(8)]-N-methyl car- 142-144 73. 5

bamic acid ester.

25 O-[5,7-dichloro quinolyl-(8)]-N-methyl 180-181 79. 3

carbamic acid ester.

26- O-[5chloro-7-iodoquinolyl- (8)1-N-methyl 149-150 60. 7

carbamic acid ester.

27 O-[5,7-diiodoquinolyl-(8)]-N-methyl car- 215-217 61. 6

bamic acid ester.

28- O-[2methyl-6-chloroquinolyl-(8)]-N- 130-133 65. 2

methyl carbamic acid ester.

29- O-[2,7-d.imctl1yl5-chloroquinolyl-(8)]-N- 154-156 63. 3

methyl carbamic acid ester.

30 O-[4-methyl-5chloroquinolyl-(8)]-N- 154-156 55. 9

methyl carbamic acid ester.

31 O-[2-methyl-5-chl0roquinolyl-(8)1-N- 137-139 58. 5

methyl carbamic acid ester.

32 O-[2-methyl-5,7-dichloroquinoly1-(8)]-N- 150-151 56. 1

methyl carbamic acid ester.

33 O-[2-methyl-5,7-dibromoquinolyl-(8)]-N 147-149 73. 5

methyl carbamic acid ester.

34- O-[6-nitr0-u uin0lyl-(8)1-N-methyl car- 192-194 58. 6

bamic acid ester.

35 O-[2-methyl-G-nitroquinolyl-(8)]-N- 141-142 49. 8

methyl carbamic acid ester.

36. O-[5-thiocyano-quinolyl-(8)1-N-methyl 135-137 40. 5

carbamic acid ester.

37- O-[5chloro7-fiuoro-quinolyl-(S)]-N- methyl carbamic acid ester.

38 O-[5-fiuoro-quinolyl-(8)]-N-methyl carbamic acid ester.

39- 0-[5-cy ano-quinolyl-(S)]-N-methyl carbamic acid ester.

40- O-[6-amino-quinolyl-(8)1-N-methyl carbamic acid ester.

1 With decomposition.

Example 41 5.2 parts of 2,6-dimethyl-8-hydroxyquinoline are dissolved in30 parts by volume of dimethyl formamide while stirring, 7.5 parts ofanhydrous triethylamine are added and, while cooling well at 10-15, asolution of 4.5 parts of methyl carbamic acid chloride and 1.5 parts ofmethyl isocyanate in 15 parts by volume of dimethyl formamide is addeddropwise within 15 minutes. The reaction is complete after stirring for6 hours at room temperature. The completion of the reaction isdetermined again by the colour reaction with ferric chloride solution asdescribed in Example 1. The yellow liquid is poured into 500 parts ofwater While stirring. After 1 /2 hours, the solid reaction product isfiltered 011 under suction, washed with water and then dried in vacuo.0n recrystallising from abs. benzene, O [2,6 dimethyl-quinolyl-( 8)]-N-methylcarbamic acid ester is obtained which melts at 140-142. Theyield is 60.8% of the theoretical.

The compounds given in the following table are also obtained by themethod described in Example 41.

Ex. Compound M.P., Yield, No. 0. Percent 42-O-[4-methyl-quinolyl-(8)1-N-methyl car- 149-151 57. 8

barnic acid ester.

43 O-[6-methyl-quino1yl- (8)1-N-methyl 142-144 60. 1

carbamic acid ester.

44 0-[2-methyl-7-allyl-quinolyl-(8) l-N-methyl 134-136 42. 9

carbamic acid ester.

45 O-[6-chloroquinolyl-(8)]-N-methy1 car- 136-139 58. 1

barnic acid ester.

46 O-[3-methyl-5chloroquinolyl-(8)]N- 160-161 61. 2

methyl carbamic acid ester.

47 O-[5-chloro-7-methyl-quinolyl-(8)1-N- 144-145 60. 4

methyl carbamic acid ester.

48- O-[5,7-dichl0ro-6methyl-quinolyl-(8)]N- 172-173 24. 5

methyl carbamic acid ester.

49 O-[2,6-dimethyl-5,7-dichloroqui11olyl-(8)]- 157-158 64. 6

N-methyl carbamic acid ester.

50 0-[2-methyl-5,6,7-trichloroquinolyl-(8)1- 152-154 63. 8

N -rnethyl carbamic acid ester.

51- O-[2-methyl-5-methoxy-quinolyl-(8)1-N- methyl carbamic acid ester.

52- O-[2,6-dimethyl-7-eth l-quinolyl-(8)]-N- methyl carbamic acid e er.

53 0-[7-benzyl-quin0lyl- (8)1-N-methyl earhamic acid ester.

54- 0-[7-(4-chlorobenzyl)quinolyl(8)]-N- methyl carbamic acid ester.

55- O-[7-(2-bromobenzoyl)-quinolyl-(8)]-N- methyl carbarnic acidester.

Example 5 6 150 parts of 2-rnethyl-8-hydroxyquinoline are dissolved in1500 parts of benzene, and a solution of 57 parts of methyl isocyanateand 15 parts of triethyl amine is added dropwise to this solution. Themixture is allowed to stand for 16 hours at 20 to 24. Completion of thereaction is determined in the manner described in Example 1 by means ofa solution of ferric chloride. The separatedO-[Z-methyl-quinolyl-(S)]-carbamic acid ester having a melting point of136 to 137 (decomposition) is sucked 011 and washed with a smallquantity of cold benzene. By recrystallization from absolute benzene aproduct of melting point 137 to 138 (decomposition) is obtained. Theyield is 65% theoretical.

The fungicidal agents are produced by methods known per se by thoroughlymixing and milling the active substances of general Formula I withsuitable carriers optionally with the addition of adhesives, dispersingagents or solvents which are inert to the active substances. Theseagents can be used in the following forms:

Solid forms: Dusts, sprinkling agents, granulates (coated granules,impregnated granules, homogeneous granules);

Water dispersible concentrates of active substances: wettable powders,pastes, emulsions;

Liquid forms: solutions; and

Forms for the production of aerosols, fogs and fumigants.

To produce the solid forms for use (dusts and sprinkling agents,granulates), the active substances are brought on to solid carriers suchas talcum, kaolin, bole, loess, chalk, ground limestone, limestone,attaclay, dolomite, diatomaceous earth, precipitated silicic acid,alkaline earth silicates, sodium and potassium aluminium silicates(feldspar and mica), calcium and magnesium sulphates, magnesium oxide,milled plastics, fertilizers such as ammonium sulphate, ammoniumphosphates, ammonium nitrate, urea, etc., and also ground vegetableproducts such as bark dust, sawdust, ground nutshells, bran, cellulosepowder, residues of plant extractions, active charcoal, etc. Thesecarriers can be used alone or admixed with each other.

The particle size of the carriers is, for dusts up to about 100p, forsprinkling agents from about 75p.0.2 mm., and for granulates from 0.2mm.1 mm. (and coarser).

As a general rule, the concentration of active substances in the solidpreparations is from (1.5-%.

To these mixtures of active ingredient and carriers can also be addedadditives which stabilise the active substance and/or non-ionic, anionicand cationic surface active substances which, for example, improve theadhesion of the active substances on plants and plant parts (glues,adhesives) and/ or attain better wettability (wetting agents) anddispersibihty of the active substances. 'Examples of such surface activesubstances are as follows: olein plus hydrate of lime, cellulosederivatives of a medium degree of viscosity (methyl celluloses,carboxymethyl celluloses, hydroxyethyl celluloses), galactomans (guargum), their anionic and cationic derivatives, polyethylene glycol ethersof monoand di-alkyl phenols (having -15 ethyleneoxide radicals permolecule and 8-9 carbon atoms in the alkyl radical, e.g. the commercialproducts known under the names Triton, Ipegal, Terpitol, etc),condensation products of ethylene oxide/ propylene oxide (mediummolecular weight of the polyoxypropylene part: 1750; e.g. the commercialproducts known by the name Pluronics), solid, liquid sulphite wasteliquor, alkali metal and alkaline earth metal salts thereof, mineraloils and polyethylene glycol ethers (carbowaxes), fatty alcoholpolyethylene glycol ethers (having 5-20 ethylene oxide radicals permolecule and 8-18 carbon atoms in the fatty alcohol moiety; e.g. thecommercial products known by the name Genapol), dextrins, caseins, theircalcium salt, proteins, polyvinyl pyrrolidones, polyvinyl alcohols (e.g.the commercial product known as Moviol), condensation products ofureaformaldehyde and also latex products.

In some cases it is necessary to add to these forms for application,plant, animal and mineral oils as penetrating agents, i .e. agents whichhelp and improve the penetration of the active substance into the plantsand parts thereof.

The concentrates of active substance which can be dispersed in water:wettable powders, pastes and emulsion concentrates, are agents which canbe diluted withwater to any concentration desired for application toplants and parts thereof, They consist of active substance, carrier,additives which stabilise the active substance, surface activesubstances, protective colloids and anti-foam agents and, optionally,solvents. The concentration of active substance in these agents is 580%.

Wettable powders and pastes are obtained by mixing and milling theactive substances with surface active substances and pulverulentcarriers in suitable mixers and milling machines until homogeneity isattained. Carriers are, for example, those mentioned in the paragraphdealing with solidzforms for application. In some cases it isadvantageous to use mixtures of carriers. By;surface active substances,glues or adhesives, wetting and dispersing agents and protectivecolloids are to be understood. Of

the glues and adhesives already mentioned, because of their properties anumber thereof can be used as so-called auxiliary dispersing agents.Other dispersing agents and wetting agents which can be used are:

Condensation products of sulphonated naphthalene and naphthalenederivatives with formaldehyde (e.g. the commercial product Sellasol),condensation products of naphthalene and derivatives thereof with phenoland formaldehyde (the commercial products known as Irgatan), alsoaluminium salts of lignin sulphonic acids, further alkylarylsulphonates, alkali metal salts and alkaline earth metal salts ofdibutyl naphthalene sulphonic acid, fatty alcohol sulphates such assalts of sulphated hexadecanols, heptadecanols, octadecanols,octadecenols, the sodium salt of sulphated hexadecyl glycol others (thecommercial products known as Eriopon), the sodium salt of oleyl methyltauride (the commercial products known as Arkopon), ditertiary acetyleneglycols (the commercial products known as Surfynol), dialkyldilaurylammonium chloride (the commercial product known as Aliquat), and fattyacid alkali metal and alkaline earth metal salts. Examples of anti-foamagents are: silicones, Antifoam A, etc.

. The active substances are so mixed, milled, sieved and strained withthe additives mentioned above that the solid particle size in wettablepowders is 20-40 and inpastes is not more than 3 1.. To produce emulsionconcentrates and pastes, liquid dispersing agents such as those given inthe previous paragraphs, organic solventsand water are used. Examples ofsolvents are: alcohols, benzene, xylenes, toluene, dimethyl sulphoxide,dimethyl formarnide and mineral oil fractions boiling between 120 and350 C. The solvents must be almost without smell, not phytotoxic, inertto the active substances and not easily inflammable.

The forms for application which can be dispersed in water can alsocontain other additives to increase the stability to light, alsopenetrating agents, anti-foam agents and also synergists.

The wettable powders, pastes and emulsion concentrates are diluted withwater to the practical concentrations desired which are between 0.01 and2%, calculated on the active substance. In the composition andconcentration for use described, these application forms have goodsuspendibility which can be further improved, e.g. by addition ofsynthetic voluminous silicic' acid. The emulsifiable property of theemulsion concentrates is also very good.

In addition, the agents according to the invention can be in the form ofsolutions or sprays. For this purpose the active substances of generalFormula I can be dissolved in suitable organic solvents, mixtures ofsolvents or in water. In particular, higher aliphatic and aromatichydrocarbons, chlorinated derivatives thereof, alkyl naphthalenes aloneor mixed with each other or with water can be used as organic solvents.The solutions preferably contain the active substances in aconcentration from 1 to 20%. They are used in the form of spray or mistwith suitable spraying or mist blowing equipment.

So-called aerosols can be produced from solutions of the activesubstances by the addition of propellants; aerosols are particularlysuitable for use in the house and garden. Both the solutions and theaerosols can contain additives to increase the adhesion, resistance torain and light and also vegetable, animal and mineral oils to improvethe adhesion and penetration.

Also, the active substances of general Formula I can be worked up with acombustible substance, e.g. sawdust or paper and a source of oxygen suchas potassium chlorate and potassium nitrate, to form a fumigant orfumigant paper. 7

The application forms described can be mixed very well with otherbiocidally active compounds or agents. Thus to broaden the range ofaction in the agents according to the present invention, otherbiocidally active substances such as insecticides, fungicides,bactericides, fungistatics, bacteriostatics or nematicides can bepresent. The agents according to the invention can also containfertilizers, plant hormones, etc.

To increase the stability of the active substances it is of advantage toadd, either by mixing in, by diluting or by dispersing, additives whichregulate the pH value of the preparations which are to be diluted withwater or contain water as solvent.

The following examples describe the production of various forms forapplication of the fungicidal agents according to the invention. Partsare given therein as parts by weight.

EXAMPLE I Dust ester l0 Highly dispersed silicic acid 5 Talcum are mixedtogether and milled. This l0% dust is used for the disinfection of seedbeds.

Parts ethyl-quinolyl-(S)]-N-methyl-carbamic acid ester Talcum areintimately mixed together and milled. A 2% dust is obtained which isused for the treatment of seed beds.

EXAMPLE II Granulates Parts 0 [5 acetyl-quinolyl-(8)l-N-methyl-carbamicacid ester Highly dispersed silicic acid 3 Ground limestone (particlesize 0.4-0.8 mm.) 87 Carbowax 5 The ground limestone is evenlyimpregnated with the carbowax. These particles are then mixed with themixture consisting of the active substance and highly dispersed. silicicacid, and milled.

The active substance is mixed in a mixing apparatus with the carriersand the parafiin as distributing agent.

The pulverulent dressing agent obtained is then milled and used for thetreatment of seeds of all types.

EXAMPLE IV Wettable powder Parts 0 [5,7 dichloro quinolyl (8)] N methylcarbamic acid ester Cetyl polyglycol ether 5 Naphthalene sulphonicacid/formaldehyde condensation product 5 Highly dispersed silicic acid 5Adhesive 1 Kaolin 34 O [4 methyl quinolyl (8)] N methyl-car- The activesubstances are finely mixed with the carriers and distributing agentsgiven for each and milled. A 50% or a 65% wettable powder respectivelyis obtained, the wettability and suspendability of which are excellent.

1 0 On diluting these Wettable powders w1th water, suspensions areproduced which are suitable for the treatment of fruit trees.

EXAMPLE V Pastes Parts 0 [6 nitroquinolyl 8)] N methyl carbamic acidester 50 Nonylphenol/ethyleneoxide condensation product having 8 to 10ethyleneoxide groups l4 Spindle oil 3.5 Soap powder 0.5 Water 32 Theactive substance is intimately mixed with the additives in a mixingapparatus. This mixture is then milled on a roller mill. A 50% paste isobtained which, before use as fungicide, can be diluted with water toany concentration desired.

EXAMPLE VI Emulsion concentrate Parts 0 [5 methyl quinolyl (8)] N methylcarbamic acid ester 10 Xylene 55 Dimethyl formamide 32 Mixture ofemulsifying agents: alkylaryl polyethyleneglycol-alkylarylsulphonate-potassium salt Phytofungicidal test A. SPORE GERMINATION TESTThe fungicidal activity of the active ingredients of the general FormulaI Was determined by a spore germination test with spores of thefollowing types of fungi:

Alternaria tennis Botrytis cinerea Clasterosporium c. Coniothyrium dipl.

F usarium culmorum Mucor spec. Penicillium spec. Stemphylium cons.

A determined amount of a 1%, 0.1% and 0.01% acetone solution of theactive ingredient is placed on 2 glass slides of exactly the same size,under the same conditions. The solvent is evaporated off and a uniformcoating of active ingredient which can be inoculated is obtained on theglass slides. The slides inoculated with fungi spores are then kept indishes at room temperature in an atmosphere which is almost saturatedwith steam. After 23 and 4-6 days, the germinated spores are counted.

The concentrations of active ingredient are given in the following tablewhich inhibit at least of germination.

+ in the following table shows an at least 90% inhibition of germinationeffected by the residue of l ccm. of a 1% acetone solution of activeingredient,

++-shows the same effect attained by the residue of l ccm. of a 0.1%acetone solution of the active ingredient,

+++ shows an at least 90% inhibition of germination attained by theresidue of 1 ccm. of a 0.01% acetone solution of active ingredient.

SPORE GERMINATION TEST Compound Altern. Botr. C'last. ('onioth Fusar.Mucor Penic. Stemph.

ten. cin. c. dipl. culm. spec spec. cons.

-3- th 1- in lyls) N- eth 1 bam'c acd ster O-ier net hy i uiiioly l-(flrne h arbai'nie i013 ester O-[&ethyl-quinolyl-(8)1-N-methyl carbamicacid ester O-[S-acetyl-quinolyl-(8)]-N-methyl carbamic acid esterO-[-n-butyryl-quinolyl-(8)1-N-methyl carbamic acid esterO-[5-isovaleryl-quinoiyl-(8)]-N-n1ethy1 carbamic acid ester0-[5-benzoy1-quinolyl-(8)]-N-methyl carbamic acid ester.0-[5-(2,5'-dibromobenzoyl)-(8)]-N-methyl carbamic acid esterO-[2-methyl-5-acetyl-quinolyl-(8)]-N-n1ethy1 carbamic i est O-[Zqnethyl5-1sovalery ethyl carbamto acid esterO-[5,7-dichloroquinolyl-(8)]-Nmethylcarbamicacidester-0-(5,7-dibromoquinolyl-(8)]-N-methyl carbamic acid esterO-[5,7-diiodoquinolyl-(8)]-N-methyl carbamic acid ester.O-[5ch10ro7-iod0quin0lyl-(8)]-N-methyl carbamic acid ester ll +1-O-[4-methyl-quinolyl-(8)]-N-n1ethy1 earbamic acid ester" +4-O-[6-chloroquinolyl-(8)1-N-methyl carbamic acid esterO-[2-methyl-5,7-dichloroquinolyl-(8)]-N -metl1yl carbamic acid esterO-[5-thiocyano-quinolyl-(S)-N-mcthyl carbamic acid ester rO-[6-nitroquinolyl-(8)}N-methyl carbamic acid ester B. SEED DRESSINGTEST What is claimed is:

1. A compound of the formula: A pulverulent seed dressing 1s produced bymix ing 20 parts of the active substance to be tested with 80 parts oftalcum or by impregnating 80 parts of talcum with the acetone solutionof 20 parts of active substance. Q X

F usarz'um culmorum test Y Grains of rye are inoculated with Fusariumspores. Z R 5 g. of these grains are weighed and dusted with 10 mg. O CNHCHZ of the seed dressing described above.

The grains are then spread out on a filter paper and 40 a control ismade after 3, 4, 5, 6, 7 and 10 days. The percentual activity is addedand divided by the number of controls made. wherein T illetiat 'ticitest n R is a member selected from the group consisting of Grains ofwheat are inoculated with Tilletia spores. hydrogen and methyl 5 g. ofthese grains are then dusted with 10 mg. of the X 15 a member selectedfrom the group conslstmg of above seed dressing. The treated Wheatgrains are set in hydrogen and lower alkyl, earth containing no f i Thegerminated grains are Y 1s a member selected from the group consistingof removed after 5 days. After another 5 days the earth hydrogen loweralkyl, lower alkoxy, alkanoyl of is tested for fungi and growth thereofwhich have been from 2 to 12 carbonfltoms: beflzoyl P P f carried by thei f t d Wheat grail bromobenzoyl, chlorine, bromine, fluorine, iodine,

The action is estimated visually and is given in per-Pltmrthlocyanocyano and ammo centags- Z 1s a member selected from thegroup consisting of hydrogen, chlorine, bromine, fluorine, iodine,methyl, SEED DRESSING C NT 20%) ethyl, allyl, benzyl, chlorobenzyl' andbromobenzyl,

and P r nt ti n Q is a member selected from the group consisting ofCompound agamst hydrogen, chlorine and bromine.

Fusarium TiZZetia cal. tritici 2. A compound as claimed in claim 1 whichis O-[S- o-lfi-raiitrttl-quinolyl-(8)] N-methy1carbamic 33methylquinolyl-(8)]-N-methyl carbamic acid 1elster.

aci 3. A compound as claimed in claim 1 whic is O-[S- 0-5- hl ll-8- th tiimfii 59 100 acetylquinolyl-( 8)]-N-methy1 carbarmc acid ester.O'[5'7'$1ibTPmquin1Y1'(8)Phi-methylcar 4. A compound as claimed in claim1 which is O-[S- bannc acid ester 0. 69 100 o-s-cnlorq-g-imgo 01 -(s-methylcar-' 7 00 benzoylqurnolyl-(S)]-N-methyl carbamlc acid ester.

8. ac 6S er n n n O{552237a1ry1 quim1y1 (8)] N methy1can 5. A compoundas claimed in claim 1 Wh1ch 1s O-[5,7-

bamic acid ester d1ch1oroqu1no1y1-(8)]-N-methy1 carbamic acid ester.iiiit.itf%f?3%i@!1 11????ftflif fi 53 50 70 A cempound as claimed inclaim; 1 h is 9 e y1-q y )lyl methylqu1nolyl-( 8) -N-methyl carbamlcacid ester. carbamic acid ester 83 90 0-[2.memy1. 5,74ich19mquinolyl.(g)].N- 7. A compound as claimed in clalm 1 WhlCh 1sO-[6- offfiiiliifiitfyfiiffiiiiisn siirrrga*- 53n1troquinolyl-(8)J-N-methyl carbamic acid ester.

carbamic acid ester 50 8. A compound as claimed 1n clalm ,1 whlch 1sO-[2- methylquinolyl-(8)J-N-methyl carbamic acid ester.

13 14 9. The non-phytotoxic addition salts of the compound OTHERREFERENCES of clalmlwlthanacld' Frear: Chemistry of the Pesticides, VanNostrand,

3rd ed. p. 301 (1955). References Cited Horsfall: Fungicides, ChronicaBotanica, p. 135 and UNITED STATES PATENTS 5 p. 151 (1945). 2,681,8798/1949 Gysin et a1. 167-33 2,749,347 6/1956 Kreysa 260287 ALEX MAZEL,Pnmary Examller- 3,005,823 10/ 1961 Kaeding 260287 DONALD G. DAUS,Assistant Examiner.

1. A COMPOUND OF THE FORMULA:
 4. A COMPOUND AS CLAIMED IN CLAIM 1 WHICHIS 0-$(5BENZOYLQUINOLYL-(8)$)-N-METHYL CARBAMIC ACID ESTER.